Various Concentrations of Carbon Nanodots Induced Fluorescent

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Various Concentrations of Carbon Nanodots Induced Fluorescent Calcite with Multi-morphologies Xiuping Tang, Xue Liu, Yu Hou, Long Cai, Lijiang Chen, Qiuhua Wu, Jie Yi, and Guolin Zhang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00722 • Publication Date (Web): 18 Oct 2018 Downloaded from http://pubs.acs.org on October 18, 2018

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Crystal Growth & Design

Various Concentrations of Carbon Nanodots Induced Fluorescent Calcite with Multimorphologies Xiuping Tang,† Xue Liu,†,* Yu Hou,† Long Cai,† Lijiang Chen,‡ Qiuhua Wu,† Jie Yi,† Guolin Zhang†,* †Liaoning

Province Key Laboratory for Green Synthesis and Preparative Chemistry of Advanced Materials, College of Chemistry,

Liaoning University, Shenyang 110036, PR China. ‡

College of Pharmacy, Liaoning University, Shenyang 110036, PR China. which can control the nucleation of the inorganic phase through

ABSTRACT: Biomineralization is an important approach to

stereochemical recognition and molecular binding effects.

prepare biomimetic materials. Mineralized materials with

Considering these natural processes, researchers have focused

hierarchical structures and superior properties require special

on applying natural or synthetic nanomaterials to induce

templates to induce biomineralization. In this work, we utilized

biomineralization.1, 22

fluorescent carbon nanodots (CDs) as the templates to induce

Carbon nanodots (CDs) are a new member of organic carbon

the mineralization of CaCO3. Some uncommon morphologies

nanomaterials with interesting optical, chemical and biological

of calcite crystals have been observed with the increase of CDs

properties.23 The surface of CDs is composed of considerable

concentration, including pseudo-dodecahedron calcite, twin-

amounts of nitrogen and oxygen-containing functional groups,

grown crystalline aggregates, and so on. The CDs can occlude

which can be utilised to bind to inorganic ions and generate

within CaCO3 in specific zones through monitoring their

stabilised precursors for biomineralization. With these

fluorescence.

beneficial characteristics, CDs are very suitable templates for biomineralization. CDs have been applied to prepare

Introduction Biomineralization is a natural strategy to synthesise materials with

hierarchical

structures

and

superior

mechanical

properties.1-2 Biomineralization research can elucidate the mechanism of biomineral formation and provides a basis for the preparation of advanced biomimetic materials.2-4 Among various biominerals, CaCO3 is the most abundant and important substance which is involved in protection or structural support for different living organisms.5-7 CaCO3 is also a widely studied biomineral model in laboratories.8-11 Interesting and diverse morphological characteristics can be exhibited by regulating and controlling the biomineralizing conditions of CaCO3. Biomineralization is achieved by using organics to manipulate and produce inorganic materials.12 Organics play an important role in biomineral formation.13, 14 Various organics, including small molecules and macromolecules, have been applied as templates to induce biomineralization and obtain encouraging results.15-20 In nature, the organic templates in biomineralization generally present extraordinarily complex and hierarchical structures.19 These organic templates are assembled by proteins, polysaccharides, or glycoproteins,

fluorescent hybrid phosphors, such as CDs/CaCO3 and CDs/BaSO4.24-26 These hybrid phosphors exhibit excellent thermal and photostability solid-state fluorescence. However, the detailed crystal morphology was never investigated in these reports. Applying the fluorescence property of the CDs, the forming mechanisms can be investigated about the CDs occlusion within mineral. This study applies CDs as a template for CaCO3 mineralization. Herein, the CDs templates were prepared using citric acid and glycine as carbon sources in a simple microwave pyrolysis approach. CaCO3 mineralization was performed in the presence of CDs via a classic CO2 gas diffusion technique. Calcite crystals with uniform and multiplex morphologies were observed. The concentration of CDs played a key role in the formation of calcite with various morphologies. Fluorescence was applied to monitor the morphology of CaCO3 crystals and investigated the forming mechanism of CDs occlusion within CaCO3. Experimental Section Materials

ACS Paragon Plus Environment

Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 8

Glycine (99%), citric acid (99.5%), quinine sulfate, calcium

TU-1900

chloride anhydrous (CaCl2, 96%) and ammonium carbonate

Fluorescence measurements were performed using Cary Eclipse

were purchased from Alfa Aesar. All the other reagents were

(Shimadzu, Japan). The excitation and emission slit were set as

purchased from Sinopharm Chemical Reagent Corp. (Shanghai,

5 nm and 5 nm, respectively. The morphology and

China). Ultra-pure water was prepared by a Millipore Milli-Q

microstructure of the CaCO3 were examined by scanning

system and used throughout.

electron microscopy (SEM) on a JSM-7000F (JEOL, Japan).

Synthesis of CDs

All samples were coated with gold by sputtering prior to

CDs was prepared from glycine via a one-step microwave

observation. Powder XRD spectra of the samples were

treatment. In a typical synthesis, 1.0 g citric acid and 0.3 g

measured on D8 ADVANCE (Burker, Germany). Fluorescence

glycine were dissolved in 10 mL ultra-pure water and then the

images of the CaCO3 were observed with an inverted

solution was heated in a domestic microwave oven (700 W) for

fluorescence microscope (Nikon, Japan).

4 minutes. The resultant CDs were dispersed and dialyzed

Results and Discussion

against ultra-pure water through a dialysis membrane (MWCO

The structural information of the as-prepared CDs is shown in

= 0.1-0.5 KD, Spectrum Laboratories) for 48 h to remove the

Figure 1. The CDs are spherical nanoparticles with an average

excess precursors and resulting small molecules.

size of 5 ± 0.4 nm. The graphitic structure can be observed in

CaCO3 mineralization assistance by CDs

the magnified TEM image. Furthermore, the functional groups

The crystallization of CaCO3 was performed by adopting the

on the CDs can be determined from the FTIR spectrum of CDs.

CO2 vapor diffusion method. Firstly, CDs aqueous solution with

The broad bands at 3395 and 3217 cm-1, as well as the intense

different concentrations (0.01, 0.1, 0.5, 1.0 and 2.0 mg/mL,

peak at 1710, 1430 and 1177 cm-1, indicate that abundant

respectively) was prepared. 0.022 g of CaCl2 was added into 10

carboxylic and amide groups are present on the surface of

mL of CDs aqueous solution with different concentrations and

CDs.27 These functional groups are beneficial for CaCO3

then the solution was stirred for 30 min. The goal was for

mineralization by selectively binding to CO32− and Ca2+. The

integrated of Ca2+ ions onto the surface of CDs by

UV–Vis spectra of CDs in Figure 1c show typical optical

electrostatic interaction. The solution was transferred to a small

absorption in the UV region. Since the precursor structure of

beaker with a piece of conductive glass (0.5 cm × 0.5 cm) and

CDs is similar to the polycyclic aromatic hydrocarbons, the

placed in big beaker (1 L), where they were exposed to

absorption peak of the CDs at about 340 nm represents the

ammonium carbonate vapor. For comparison, the small beaker

typical π–π*transition of C=C bonds.

spectrophotometer

(Purkinje

General,

China).

was only contained the CaCl2 solution. After, the big beaker was covered with parafilm and stood at 25oC. After 24h of incubation, the glass substrate was taken out and rinsed with water and anhydrous ethanol three times. Finally, they were allowed to dry at room temperature for characterization. Characterization The morphology and microstructure of the CDs were examined by high-resolution transmission electron microscopy (HRTEM) on a JEM-2100 (JEOL, Japan) with an accelerating voltage of 200 kV. The samples for HRTEM were made by dropping an aqueous solution onto a 200-mesh copper grid coated with a lacy carbon film. The grain diameter and size distribution of the CDs were gotten using a Malvern Nano ZS instrument. The Fourier transform infrared spectra (FTIR) of the samples were

Figure 1 a) HRTEM image of CDs; b) FTIR spectrum of CDs; c) UV-Vis

measured on a Spectra One (Perkin-Elmer, America).

absorption spectrum of CDs; d) Excitation-dependent PL spectra of CDs. Inset

Ultraviolet–visible (UV–vis) tests were performed through a

in (a) size distribution of CDs; (d) normalized PL spectra of the CDs.


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Figure 1d shows the fluorescence emission spectra of CDs

mg/mL, respectively. The SEM images present the most

upon excitation with the different excitation wavelength. The

frequently obtained CaCO3 crystal morphology at the given set

PL emission spectrum CDs in aqueous solution exhibit a peak

of experimental conditions.

centered at 470 nm when excited by 400 nm light. The

form a stable structure within 24 h, and further incubation no

florescent quantum yield (QY) of the CDs was monitored using

longer affects the CaCO3 crystal morphology (Figure S2).

a comparative method. The maximum emission location of CDs

phase compositions of the mineralized CaCO3 products can be

is similar to that of quinine sulfate, and therefore we took

confirmed through P- XRD tests. The resulting CaCO3 crystals

quinine sulfate as the reference substance to determine the QY

yield diffraction peaks identical to those of calcite (ICDD #05-

of CDs. Absolute values were calculated according to the

0586) and no other peaks are found. These results indicate that

equation

28.

The QYs of the CDs is 17%.

To further prove that

Ca2+

CDs-induced CaCO3 crystal can The

the phase compositions of CaCO3 crystals with various

ions can be attracted onto the

morphologies are pure calcites.14 As the CDs concentration

surface of CDs through electrostatic interaction, dynamic light

increases, the CaCO3 morphology remarkably changes. Few

scattering (DLS) measurement is performed to prove the

CDs templates (≤0.01 mg/mL) in the mineralization system

interaction between CDs and

ions in solution (Figure 2).

cannot interact with CaCO3 components. Therefore, only single

is added into CDs solution, the size distribution with

well-faceted rhombohedral particles with smooth surfaces exist

the mean diameter from 5 to 274 nm. The zeta potential of CDs

in the solution (Figure 3a), and this morphology characteristic

solution is measured to be −25 mV.

is typical

When

Ca2+

Ca2+

Ca2+

The zeta potential of the

-treated CDs changes to +10 mV, which would favor

further electrostatic assembly between CDs and

Ca2+ ions.

of calcite. However, a pseudo-dodecahedron

morphology is formed when the CDs concentration is increased to 0.1 mg/mL (Figure 3b). The

formation mechanism of

calcite crystals with pseudo-dodecahedron morphology remains controversial and requires further clarification. Nevertheless, this mechanism possibly involves various processes, including selective adsorption of additives on the expressed faces, inhibitory effect of additives on the step-growth, or a combination of these phenomena.29, 30 With a further increase in the CDs concentration, an apparent ‘flattening’ phenomenon appears to the pseudo-dodecahedron CaCO3 crystal (Figure 3c). The ‘flattening’ phenomenon is just a modification of the CaCO3 crystal to a greater extent, and in essence these crystals Figure 2 After Ca2+ is added into CDs solution, size change of CDs at 25 °C

remain pseudo-dodecahedron31.

monitored by DLS (black: CDs; red: CDs@Ca2+).

Before investigating the influence of CDs on CaCO3 mineralization, we first monitored CaCO3 mineralization in the presence of the carbon source of the as-prepared CDs. In the presence of citric acid and/or glycine, CaCO3 mainly appears as single crystals with a rhombohedral morphology (Figure S1). However, when a specific concentration of CDs was added, the CaCO3 crystal morphology underwent transition from rhombohedra to spherical crystal aggregates (Figure 3a-e). This finding confirms that CDs participate in the phase formation of CaCO3 crystal. Figure 3 shows the SEM images and P-XRD patterns of the CaCO3 crystal mineralized for 24 h at a specific CDs concentration of 0.01, 0.1, 0.5, 1.0 and 2.0



Page 4 of 8

aggregations (Figure 3d). Two crystalline aggregations hold each other via an obvious junction (Figure 3d’). As the CDs concentration further increases, more CO32− and Ca2+ ions become adsorbed, and more CaCO3 crystals are formed and packed on the crystalline aggregations. The junction can no longer support the twin-grown crystalline aggregations. Therefore, the twin-grown crystalline aggregations separate into stabilized and individual spherical crystalline aggregation with low surface energy (Figure 3e).

Figure 3 Scanning electron microscope (SEM) images and powder X-ray diffraction (P-XRD) patterns of the CaCO3 mineralized products obtained in the presence of different concentrations of CDs (a=0.01, b=0.1, c=0.5, d=1.0 and

Figure 4 Fluorescence images of the CaCO3 mineralized products obtained in

e=2.0 mg/mL, respectively). The right-column (a’- e’) images are the magnified

the presence of different concentrations of CDs (From left to right: 0.01, 0.1,

versions of the left-column (a-e) ones.

0.5,

The growth mechanism of CaCO3 crystals occurs toward more complex forms when more CDs were added to the system. The interaction between CDs and CaCO3 components induces

1.0

and

2.0

mg/mL,

respectively)

are

observed

through

inversion fluorescence microscope under normal light, UV and blue irradiation, respectively. The scale bar is 50 μm.

In addition to serving as an effective template to mediate the

ion

biomimetic mineralization of CaCO3, CDs can also act as a

binding. The interaction is strong enough to disrupt the

phosphor to render CaCO3 fluorescent properties (Figure 4).

formation of typical calcite solids and promote the appearance

The

of new aggregations resulting from flat rhombohedra stacked

an inversion fluorescence microscope. The zoning of the CDs

together to reduce their interface energy (Figure 3d and 3e). In

under the growth sectors are clearly seen in the rhombohedral

addition, a spiral mechanism dominates the stacking process

and pseudo-dodecahedron CaCO3 crystals. There sites can be

and thus produces asymmetric polygonised growth hillocks

regarded as the kink sites on a growing crystal face that provides

composed of two pairs of non-equivalent vicinal faces.32 The

the most favourable environment for binding of the CDs.

spiral

Besides, from these images, CaCO3 monocrystalline (including

various supersaturating regimes through CO3

2−

growth

further

generate

and

twin-grown

Ca2+

crystalline

CaCO3


crystals

are

observed

under

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well-faceted

rhombohedral

dodecahedron

monocrystalline

monocrystalline, and

flattening

pseudo-

aged Innovative Talents of Liaoning Province of China

pseudo-

(RC170258)

dodecahedron monocrystalline) and isotropic polycrystalline

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Page 8 of 8

For Table of Contents Use Only

Various Concentrations of Carbon Nanodots Induced Fluorescent Calcite with Multimorphologies Xiuping Tang,† Xue Liu,†,* Yu Hou,† Long Cai,† Lijiang Chen,‡ Qiuhua Wu,† Jie Yi,† Guolin Zhang†,*

Carbon dots (CDs) can act as a phosphor to render CaCO3 fluorescent properties. Some uncommon morphologies of calcite crystals have been observed with the increase of CDs concentration, including pseudododecahedron calcite, twin-grown crystalline aggregates, and so on.


Various Concentrations of Carbon Nanodots Induced Fluorescent

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